CN1041833C - Gas polymerization process of alpha alkene - Google Patents

Gas polymerization process of alpha alkene Download PDF

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CN1041833C
CN1041833C CN93102676A CN93102676A CN1041833C CN 1041833 C CN1041833 C CN 1041833C CN 93102676 A CN93102676 A CN 93102676A CN 93102676 A CN93102676 A CN 93102676A CN 1041833 C CN1041833 C CN 1041833C
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polymer
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carbon atoms
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CN1075484A (en
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G·戈沃尼
G·帕特龙辛尼
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Basel North America Co ltd
Basell Technology Co BV
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Montell Technology Co BV
Montell North America Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/02—Manufacture of electrodes or electrode systems
    • H01J9/18—Assembling together the component parts of electrode systems
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/901—Monomer polymerized in vapor state in presence of transition metal containing catalyst

Abstract

The present invention relates to a process for the production of polymers and copolymers of olefins CH2=CHR, wherein R is a hydrogen atom or an alkyl or aryl radical having a number of carbon atoms of from 1 to 10, comprising at least one (co)polymerization step in the gas phase, in the presence of a highly active catalyst obtained from a titanium compound supported on a magnesium halide in active form and an Al-alkyl compound. The process is characterized by the fact that it is carried out by feeding a small amount compared with the polymer of a compound having at least two groups, same or different, capable of reacting with the alkyl aluminum compound and able to selectively inhibit the reactivity of the polymer particles fine compared to the average granulometric size of the polymer present in the gas phase.

Description

α -Process for the gas-phase polymerization of olefins and polymers
The invention relates to the alkene CH2Process for the production of polymers or copolymers of CHR (in which R is an oxygen atom or an alkyl or aryl radical having from 1 to 10 carbon atoms) comprising at least one stage of gas-phase (co) polymerization carried out in the presence of a highly active catalyst prepared from a titanium compound supported on activated magnesium oxide and an aluminum alkyl. The process is characterized in that it is carried out by adding a small amount (compared with the polymer) of a compound having at least two groups which are identical or different and which are capable of reacting with the alkylaluminum compound and of selectively inhibiting (compared with the average particle size of the polymer present in the gas phase) the reactivity of the fine polymer particles.
It is known that one or more olefin polymerization processes are carried out in the gas phase in a fluidized bed or mechanically stirred bed reactor in the presence of catalysts obtained from compounds of transition metals of groups IV, V or VI of the periodic Table of the elements and of alkylaluminum compounds or based on chromium oxide catalysts.
The polymer is obtained in the form of particles of nearly regular morphology, which is related to the morphology of the catalyst; the size of the particles depends on the size of the catalyst particles and the reaction conditions, and is usually around the average value.
In these processes, the heat of reaction is removed by means of heat exchangers placed inside the reactor or in the circulation line of the reaction gases.
The problems generally encountered during the polymerization are caused by the presence of very fine polymer particles, which are generated by the already existing fine catalyst particles or by the breakage of the catalyst itself.
These fines tend to deposit on and adhere electrostatically to the inner walls of the reactor and to the heat exchangers, and subsequently, due to the growing size of the chemical reactions, cause heat transfer with low insulating effect, with the result that hot spots are formed in the reactor.
These effects are enhanced when the gas-phase α -olefin polymerization process is carried out in the presence of highly active catalysts, such as those comprising the reaction product of an aluminum alkyl with a titanium compound supported on an active magnesium halide.
Thus, a loss of fluidization efficiency and homogeneity generally occurs, for example, catalyst feed interruptions and blockages of the polymer discharge system can occur; in addition, excessive temperatures can cause the particles to melt and form a thin layer of agglomerates that adhere to the reactor walls and the agglomerates formed can clog the gas distribution plate.
These drawbacks lead to poor process reproducibility and are forced to cease operation, even after a relatively short time, by removing the deposits formed inside the reactor.
To avoid these drawbacks, several solutions have been proposed, which can be solved by influencing the catalyst activity, or by reducing or eliminating the electrostatic voltage.
Patent application EP359444 describes the introduction into the polymerization reactor of small amounts (generally less than 0.1 ppm with respect to the polymer mixture) of inhibitors selected from inhibitors or substances capable of poisoning the catalyst, in order to reduce the rate of polymerization of the olefins. However, as described in the same patent application, the use of a large amount of inhibitor adversely affects the quality and properties of the resulting polymer, such as the melt index, melt flow ratio and/or stereoregularity of the polymer, as well as reducing the efficiency of the process.
US4739015, which also lists active hydrogen-containing compounds such as ethanol, methanol, ethylene glycol, propylene glycol and diethylene glycol, describes the use of oxygen-containing gaseous products and active hydrogen-containing liquid or solid compounds to prevent the formation of agglomerates and fouling of the reactor during the preparation of heterogeneous propylene polymers.
In order not to deactivate the catalyst, these known polymerization inhibitor compounds are used in an amount of n ppm with respect to the polymer; at said concentrations, these compounds have no effect on the selective deactivation of the particles of the fining agent; at high concentrations, however, polymerization does not occur. Thus, the use of the components described in said patent does not solve the problem of inhibiting the reactivity of the fine-grained polymer particles, with consequent sticking and fouling of the reactor walls.
Various techniques have been proposed to reduce or eliminate the migration phenomena caused by static voltages and the formation of deposits on the walls.
A group of chemical additives which generate a positive or negative charge in the reactor is described in US4803251 and are added to the reactor in amounts of a few ppm per monomer to prevent the formation of undesired positive or negative charges. In this case, remediation may involve reducing polymer quality as well as reducing the productivity of the reactor.
Patent EP-B-232701 describes the use of an antistatic agent to prevent the formation of inner shells in reactors during the preparation of Ultra High Molecular Weight Polyethylene (UHMWPE), wherein the polymer is in the form of a powder having an average particle size of less than 1mm, and the antistatic agent is used to solve the problems associated with the presence of static electricity in ultra high molecular weight polyethylene powder. Preferred antistatics are mixtures of organic salts of chromium with organic salts of calcium and phenolic stabilizers, the latter having to be used in amounts of less than 200ppm, preferably from 5 to 100ppm, in order not to interfere with the catalyst activity.
The antistatic prevents the formation of an inner reactor shell. However, as is clearly shown in EP-A-362629 and EPA-364759, the polymers have ｃA rather low bulk density and the impurities are present in the film thus produced in the form of non-molten products.
These recent patents propose the pretreatment of the catalyst with antistatic agents in order to eliminate these drawbacks. For this purpose, the antistatic must not contain functional groups capable of deactivating the catalyst. It is used in amounts of several ppm by weight with respect to the final polymer and up to 1000% by weight with respect to the catalyst. By this procedure, a certain amount of impurities remains in the films made from these polymers.
EP-B-229368 describes the use of antistatic agents to prevent the formation of the inner shell of the reactor during the gas-phase polymerization or copolymerization of ethylene.
Preferred antistatics are mixtures of organic salts of chromium with organic salts of calcium and phenolic stabilizers, the latter having to be present in amounts of less than 100ppm (relative to the polymer) in order not to interfere with the catalyst activity.
Other methods of reducing or eliminating the static voltage include (1) installing a grounding device in the fluidized bed, (2) ionizing the gas or particles by electrical discharge to produce ions that neutralize the static electricity on the particles and (3) using a radioactive source to produce radiation that can generate ions that neutralize the static electricity on the particles.
However, the use of these techniques in commercial scale fluidized bed polymerization reactors is generally neither practical nor easy.
The fluidized or stirred bed consists of polymer particles of a certain geometry and particle distribution, preferably narrow and generally having a distribution value of more than 500. mu.m.
The presence of large amounts of fine particles, mainly from the partial cracking of the catalyst, can give rise to problems of adhesion of these particles to the reactor walls.
To date, none of the proposed techniques solves the problem of inhibiting the reactivity of fine polymer particles in the gas-phase polymerization of olefins carried out in a fluidized-bed system, in order to prevent the polymer from sticking to the reactor walls, which is considered to be one of the main causes of the sticking phenomenon and the defects resulting therefrom.
Thus, there is a need for solutions which do not reduce the activity of the catalyst system, (whereas inhibition of polymerization using compounds would have the opposite result), while at the same time inhibiting polymerization which would normally lead to the formation of fine particles of the rubbery oligomer.
It has now surprisingly been found that by using appropriate amounts of specific organic compounds it is possible to deactivate fine-particled catalyst particles which have been pre-existing or formed during the polymerization without reducing the polymerization yield or slowing down the process.
In this way, fouling of the reactor walls and/or clogging of the reactor feed and discharge pipes is avoided, while process efficiency and product quality are maintained.
The various additives typically used in the prior art must be used in low concentrations in order not to poison the catalyst. The compounds of the process of the invention can be used in such large amounts that they can be concentrated on the finest catalyst particles and deactivate them.
Production of alkene CH2The process according to the invention for the (co) polymerization of CHR, where R is a hydrogen atom or an alkyl or aryl radical having from 1 to 10 carbon atoms, comprises carrying out at least one gas-phase (co) polymerization step in the presence of a catalyst in a fluidized or stirred bedA solid catalyst component comprising (1) a titanium compound supported on a magnesium dihalide in active form, and optionally the product of the reaction of an electron donor with (2) an alkylaluminum compound, in the presence or absence of an electron donor, in which: the fluidized or stirred bed comprises particulate polymer particles, at least 80% of which are greater than 500 μm and less than 10% of which are less than 200 μm; and a compound (3) having a chain of at least 4 carbon atoms and containing at least two groups capable of reacting with an alkylaluminium compound, is added at any stage of the process in an amount greater than 100ppm by weight with respect to the polymer produced, the molar ratio of compound (3) to alkylaluminium compound being less than 1; the compound (3) is also selected to inhibit polymerization on polymer particles smaller than 850 μm when used in standard polymerization tests of mixtures of ethylene and propylene.
The standard test used as the evaluation criterion is described below:
during the polymerization, alkanes having 3 to 5carbon atoms are preferably present in the gas phase, said alkanes being present in an amount of 20 to 90% relative to the total gas.
As the gene capable of reacting with an alkylaluminum compound, it is desirable that the group is capable of undergoing a substitution reaction, such as a reaction, with an alkylaluminum compound
It was unexpectedly found that compound (3) preferentially aggregates on top of the small size particles. Due to the presence of the reactive group, the alkylaluminum compound is deactivated by reaction with said reactive group.
The same results are not observed when compounds containing two or more reactive groups, but with carbon chains of less than 4 carbon atoms, such as ethylene glycol or propylene glycol, are used. At low concentrations, the compounds do not inhibit polymerization on the finest particles, whereas in the range of concentrations used for the compounds of the invention, the compounds deactivate the catalyst and thus do not allow polymerization to actually take place.
Examples of compounds (3) which can be used in the process of the invention are: a) polyols containing carbon chains of at least 4 carbon atoms, preferably 4 to 8 carbon atoms, of which sorbitol and 1, 4-butanediol are preferred.
b) Hydroxy esters containing at least two free hydroxyl groups, preferably glycerol monostearate and sorbitan monooleate, prepared from carboxylic acids containing at least 4, preferably 8 to 22, carbon atoms and polyhydric alcohols.
c) General formula is CH3(CH2)nCH2-N(CH2CH2OH)2Wherein N>2, preferably between 6 and 20. Representative compounds are commercial products sold under the trademarkAtmer163 by ICI corporation.
d) Polyepoxide oils, for example epoxidized linseed oil and epoxidized soybean oil. Representative compounds are sold under the trade names Edenol B316 and EdenolD 82 by the company Henkel.
As stated, these compounds are generally added in an amount of 100 to 2000ppm, preferably 100 to 800ppm, based on the weight of the polymer, the molar ratio to the alkylaluminum compound (2) being less than 1, generally 0.05 to 0.8.
The amount of compound (3) varies within limits depending on the catalyst particle distribution (or on the particle distribution of the polymer formed, for example in the case of sequential polymerization of propylene and mixtures of propylene with ethylene, in which one or more gas-phase copolymerization steps are carried out after the propylene homopolymerization step). In general, when a large amount of fine particles is present, a large amount of compound (3) is used.
The amount of compound (3) used is also related to the nature of the compound itself, and it has been observed that, for example, compound (d) generally acts at a lower concentration than the other compounds, when all conditions are equal.
As indicated above, the gaseous phase may contain an inert C3-C5Alkane, the dosage of which is 20 to 90 mol percent of the total gas quantity, and is preferably 30 to 90 mol percent. Suitable alkanes include propane, butane, isobutane, n-pentane, isopentane, cyclopropane and cyclobutane, with the preferred alkane being propane.
The alkane may be introduced into the reactor either with the monomer or separately and recycled with the recycle gas, which is the gas stream unreacted in the bed and removed from the reaction zone, and is preferably introduced into the velocity reduction zone in the upper portion of the bed where entrained particles have had a chance to fall back into the bed. The recycle gas is compressed and then passed through a heat exchanger before it is returned to the bed. See gas phase reactors and techniques as illustrated in U.S. 3298792 and 4518750.
Examples of polymers that can be made are high density polyethylene (HDPE, density greater than 0.940 g/cm 3), including homopolymers and interpolymers of ethylene and α -olefins having from 3 to 12 carbon atoms, linear low density polyethylene (LLDPE, density less than 0.94 g/cm)3) And very low density linear polyethylenes (VLDPE and ULDPE, density less than 0.92 g/cm3And a density of 0.88 gCentimeter3) An impact resistant propylene polymer obtained by sequential polymerization of ethylene and one or more α -olefins having 3 to 12 carbon atoms, an elastomeric terpolymer of ethylene and propylene with a minor amount of a diene and an elastomeric copolymer of ethylene and propylene wherein the content of units derived from ethylene is in the range of 30 to 70% by weight, isotactic polypropylene and a crystalline copolymer of propylene and ethylene and/or other α -olefins wherein the content of units derived from propylene is above 85% by weight, and an ethylene-propylene mixture containing up to 30% by weight of ethylene.
The process of the invention is particularly advantageous for the production of LLDPE, VLDPE, ULDPE, heterophasic propylene copolymers and elastomeric copolymers of ethylene and propylene which may also contain small amounts of dienes. In these cases, in fact, but for the process of the invention, the problems of fouling of the reactor and the blockage of the feed and discharge lines of the reactor are particularly aggravated by the presence of fine rubbery particles.
In the polymer obtained by the process according to the present invention, it has been observed that the compound (3) is selectively concentrated on the polymer having a smaller size.
The compound (3) may be added at any stage during the polymerization.
The inventionAn example of the process of (1) is shown in the attached FIG. 1, which is used to produce heterophasic propylene copolymers. The apparatus comprises a contour reactor R1Which polymerizes propylene to a homopolymer in the liquid phase, and two gas-phase reactors R connected in series2And R3Wherein a gaseous ethylene-propylene mixture is copolymerized to form a rubbery copolymer which grows on the homopolymer matrix from the contour reactor. To the contour reactor R1To which liquid propylene, various catalyst components, and optionally hydrogen as molecular weight regulator are added (via line 1). The polymer suspension in the contour reactor was passed into a linear flash tube and heated with steam, in which unreacted propylene was evaporated. To this tube is added a compound (3) through line 2 in order to inhibit the subsequent formation of a rubbery copolymer on the fine particles of the homopolymer. In the cyclone separatorSeparator D1Middle, gaseous propylene (which is at E)3Is recycled into the contour reactor R after being liquefied1In) is separated from the homopolymer, which is fed to the reactor R via line 32In (1). Line 4 represents the feed line for the ethylene/propylene mixture and for hydrogen, which is fed to the reactor R via the recycle line2And R3. Reactor R2And R3Is adjusted by using a heat exchanger E1And E2And a compressor P1And P2Recycling the reaction materials. The copolymerization is carried out in two reactors R1And R2Is carried out, the final polymer produced is discharged via line 5.
Another example of a flow chart of an apparatus that can be used in the method of the present invention is shown in fig. 2. The apparatus comprises a reactor R1In which a small amount of monomer is prepolymerized in the presence of a catalyst component, and two fluidized-bed reactors R2And R3In which gas-phase polymerization is carried out. Using said device, after the prepolymerization step, the prepolymer is introduced into the first gas-phase reactor R2Before, add component (3); optionally (also advantageously) even in the first gas phase reactor R2Thereafter, the polymer formed is introduced into a second gas-phase reactor R3Before, partially addingComponent (3).
The catalyst used in the process of the present invention comprises the reaction product of 1) a solid component comprising a titanium compound supported on an active magnesium dihalide, which solid component may also comprise an electron donor compound (internal electron donor) when the solid component is used to prepare catalysts for the stereospecific polymerization of propylene, butene-1 and olefins like α, internal electron donors are generally used because high stereospecificity is required in the process to obtain an isotacticity index of greater than 90, preferably greater than 95.
2) An alkylaluminum compound, an electron-donor compound (external electron donor) may also be present. When stereoregular polymers, such as propylene polymers having a high isotacticity index, are produced by the process of the present invention, external electron donors are used to impart the high directing properties necessary for the catalyst. However, when the diethers described below are used as internal electron donors, the catalyst orientation itself is sufficiently high and no external electron donor is required.
The use of active magnesium dihalides as supports for catalysts of the Ziegler-Natta type has been described in considerable amounts in the patent literature. The role of these vectors was first described in U.S. Pat. Nos. 4298718 and 4495338.
The magnesium dihalide in active form present as support in the catalyst component used in the process of the invention is characterized by an X-ray spectrum in which the most intense diffraction line appearing in the spectrum of the non-active halide has reduced intensity and is replaced by a maximum intensity of halogen moving towards smaller angles (angles relative to the most intense line).
The preferred magnesium halide is magnesium dichloride.
Titanium compounds suitable for preparing the solid component include titanium halides, e.g. TiCl4、TiCl3And alcoholates of titanium, e.g. trichlorophenoxy and trichlorobutoxytitanium, TiCl4Is preferred.
The titanium compound can also be used together with other transition metal compounds such as mixtures of vanadium, zirconium and hafnium compounds.
Suitable internal electron donors include ethers, esters, amines, ketones and compounds of the formulaIn which R isⅠAnd RⅡIdentical or different from each other, are alkyl, cycloalkyl and aryl radicals of 1 to 18 carbon atoms, RⅢAnd RⅣThe same or different from each other, are alkyl groups of 1 to 4 carbon atoms.
Preferred compounds are alkyl, cycloalkyl and aryl esters of polycarboxylic acids, such as phthalic and maleic acids, and R as described aboveⅢAnd RⅣAre diethers of methyl.
Examples of such compounds are di-n-butyl phthalate, diisobutyl phthalate, di-n-octyl phthalate, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-isobutyl-1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane and 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane.
The molar ratio of internal electron donor to Mg is generally from 1: 8 to 1: 14. The titanium compound (expressed as Ti) is generally present in an amount of 0.5 to 10% by weight. Examples of suitable solid components are described in U.S. 4474221, 4803251 and 4302566, the preparation of which is hereby incorporated by reference.
Using the catalyst prepared from the catalyst component described in EP-A-344755, the description of which is incorporated herein by reference, spherical polymers having an average diameter of 300 to 5000 μm can be prepared, the polymers having ｃA very high bulk density in the case of ethylene and propylene.
This patent can also be used to prepare polymers having a regular geometry other than spherical. Examples of such polymers are those which can be obtained with the supports and catalysts described in patent application EP-A-449673.
The compounds described in U.S. 4472520 and 4218339 also belong to the components which can be used in the process according to the invention.
The alkylaluminum compound (2) is selected from the group consisting of trialkylaluminums such as triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum. It is also possible to use trialkylaluminums with trialkylaluminumhalides or alkylaluminum sesquichlorides (e.g. AlEl2Cl and Al2El3Cl3) A mixture of (a).
The Al/Ti ratio in the catalyst is more than 1, generally between l0 and 4000, preferably 20-800.
The external electron donor may be the same or different from the electron donor compound present as the internal electron donorA compound (I) is provided. If the internal electron donor is an ester of a polycarboxylic acid, in particular a phthalate, the external electron donor is preferably selected from those of formula R1R2Si(OR)2Wherein R is1And R2Is an alkyl, cycloalkyl, or aryl group of 1 to 18 carbon atoms. Examples of such silanes are methylcyclohexyl-dimethoxysilane, diphenyl-dimethoxysilane and methyl-tert-butyl-dimethoxysilane.
The efficiency of the process of the invention has been evaluated by means of standard tests aimed at evaluating the performance of some compounds as selective inhibitors of very fine particles.
The method consists of two-step polymerization in the same high-pressure autoclave; in the first stage, the polymerization is carried out in liquid propylene to give a propylene homopolymer, and in the second stage, after degassing, the gas-phase copolymerization is carried out on the homopolymer matrix using a mixture of gaseous ethylene and propylene, and before degassing, a certain amount of compound (3) is introduced into the autoclave.
The ability to reduce the formation of rubbery copolymers was evaluated by the ethylene content bound respectively to the fractions with particles having a diameter above 850 μm and to the fractions with a diameter below 850. mu.m.
If the ethylene content in the<850 μm fraction is much less than the fraction>850 μm content (the ratio of the fraction>850 μm content to the fraction<850 μm content is equal to or greater than 1.15), the compound (3) is considered to be an effective inhibitor and can therefore be used in the process of the invention.
The efficiency can also be evaluated by the polymerization yield, which must be the same as the level of the test carried out without compound (3) in this evaluation method.
In the polyhydrocarbons obtained by the process of the present invention, the compound (3) is accumulated on the polymer particles of smaller size, without any disadvantage in the synthesis step, and the yield is high.
The following examples further illustrate the invention but are not to be construed as limiting the invention. General procedure for preparation of the catalyst
The catalyst component (1) used in the examples was prepared as follows.
Under an inert atmosphere, 28.4 g of MgCl249.5 g of absolute ethanol, 10 ml of ROL OB/30 vaseline oil and 100 ml of silicone oil with a viscosity of 350CS are introduced into a reaction vessel equipped with a stirrer and heated at 120 ℃ until MgCl2Until dissolved. The hot reaction mixture was then transferred to a 1500 ml vessel equipped with a UIlraTurraxT-45N stirrer, which had been filled with 150 ml of vaseline oil and 150 ml of silicone oil, the temperature was maintained at 120 ℃ while stirring at 3000rpm for 3 minutes, and then the mixture was discharged into a 2 l vessel equipped with a stirrer and containing 1000 ml of anhydrous N-heptane cooled to 0 ℃. The resulting particles were recovered by filtration, washed several times with 500 ml of n-hexane each time, and the alcohol content was reduced from 3 moles to the content indicated in the various examples by gradually heating to a temperature of from 50 to 100 ℃ over a sufficient period of time.
25 g of the adduct containing the various alcohol contents specified in the examples were transferred, with stirring at 0 ℃ to a reactor equipped with a stirrer and containing 625 ml of TiCl4Then the temperature was raised to 100 ℃ over 1 hour, and when the temperature reached 40 ℃, diisobutylphthalate was added in an amount such that the molar ratio of magnesium to phthalic acid ester was 8.
The contents of the reaction vessel were then heated with stirring at l00 ℃ for 2 hours, then the stirring was stopped and the solid allowed to settle.
The hot liquid was removed by siphoning and 500 ml TiCl was added4The mixture was heated and stirred at 120 ℃ for 1 hour. Stirring was stopped, the solid allowed to settle and the hot liquid was siphoned off. The solid was washed several times with an equal amount of n-hexane at 60 ℃ and subsequently at room temperature. Examples 1 to 7
The following examples relate to standard tests aimed at evaluating the efficiency of certain compounds as inhibitors of fine particles in the process of the invention, and also to the preparation of heterophasic propylene copolymers.
The polymerization test was a test conducted in a 4-liter autoclave. After degassing and washing with propylene, the autoclave was kept at 30 ℃ under a medium stream of propylene.
By adding MgCl dispersed in hexane and containing 0.01 g of a solution prepared by the general procedure described above containing 50% by weight of ethanol2-a solid catalytic component prepared from an ethanol adduct, 0.76 g of Triethylaluminium (TEAL) and 0.018 g of diphenyl-dimethoxy-silane as external electron donor, to carry out the polymerization, followed by the addition of an amount of hydrogen to obtain a melt index "L" in the range from 2 to 6. 2.3 liters of propylene were added under stirring at normal temperature.
The temperature was raised to 70 ℃ and polymerization was carried out for 110 minutes to obtain a propylene homopolymer. The temperature was lowered to 10 ℃ and the compound (3) dissolved in 20CC hexane was injected, followed by polymerization for another 10 minutes.
At this point the stirring was stopped, the propylene was degassed to 5 bar while maintaining the temperature constant at 70 ℃, ethylene feed was added to make up for the polymerization consumption until the total pressure was 10 bar and this pressure was maintained with a pre-formulated ethylene/propylene mixture of 65/35 molar ratio. The mixture is added in an amount of 15% by weight of the final product and is finally degassed until the end.
In Table 1, in addition to the operating conditions of the copolymerization step, the ethylene content is reported in combination in the fraction of particles having a diameter greater than 850 μm and in the fraction having a diameter<850. mu.m. Comparative example 8
The preparation of the heterophasic propylene copolymers was carried out according to the procedures described in examples 1 to 7, but without any addition of compounds prior to the copolymerization step. The results in Table 1 clearly show that the ethylene content is essentially the same in the fractions with particles>850. mu.m and particles<850. mu.m. Comparative example 9
The heterophasic propylene copolymers were prepared as described in examples 1 to 7, but the compounds used as inhibitors did not contain functional groups. M100 silicone oil was used in an amount equal to 0.76 g. It was found that this compound with a molar ratio of 0.126 to TEAL affected the reaction rate without reducing the amount of ethylene bound to the fine fraction. Comparative examples 10a, 10b, 11
Comparative example 9 was repeated using a bifunctional or polyfunctional compound having less than 4 carbon atoms as an inhibitor. The amounts of monopropylene glycol and glycerol used are listed in table 1. The results reported in table 1 show that a low percentage of monopropylene glycol (propylene glycol/TEAL = 1.5 moles) is ineffective (example 10a), a higher percentage (propylene glycol/TEAL = 2.24 moles is effective but slows down the reaction significantly (example 10b), glycerol is ineffective (example 11) example 12
Polymerization tests of the heterophase copolymers were carried out in a pilot plant in order to verify the antifouling effect of the compounds selected according to the tests described in examples 1 to 11.
The device was as described in figure 1, using the inhibitor compound Atmer 163. Liquid propylene at a flow rate of 90 kg/h was prepared from MgCl containing 45% by weight of ethanol according to the general method described above2Ethanol adduct, TEAL in an amount of 0.32 g/kg propylene and an external electron donor in a weight TEAL/electron donor ratio =3, and hydrogen as molecular weight regulator in an amount of 0.02 kg/kg propylene (fed via line 1) to the loop reactor R1In (1).
The polymer suspension in the contour reactor was passed through a straight flash tube and heated with steam, in which unreacted monomer propylene was evaporated. To this tube was added Atmer163(60 kg/h) via line 2. After passing through cyclone D1, the polymer was fed at a rate of 21 kg/h (via line 3) into the first fluidized-bed reactor R2In (1). A gaseous mixture of ethylene and propylene is fed via line 4 to produce the copolymer in the gas phase containing 38% ethylene, hydrogen also being present in moles H2／C2Where = 0.014 is present. The polymerization was carried out in two reactors connected in series, producing the final polymer in an amount equal to 43 kg/h.
The polymerization conditions in the contour reactor were:
temperature 70 ℃ pressure 3000 kPa (30 bar)
Residence time 105 minutes
The polymerization conditions in the gas phase reactor were:
first reactor 2 nd reactor
The temperature is 70 ℃ and 60 DEG C
Pressure 1200 kPa (12 bar) 700 kPa (7 bar)
Residence time 62 minutes and 54 minutes
The temperature of the cyclone for the propylene/polymer separation between the periphery and the gas phase reactor was maintained at 70 ℃ and the pressure at 1400 kPa (14 bar).
The final properties of the polymer produced were: melt index "L" = 0.69 g/10 min; cast bulk density = 0.42 g/cc.
To confirm the efficiency of Atmer163, samples with a total ethylene content (relative to the polymer) equal to 27.5% by weight were taken after 4 days of run-time; the fraction with particles larger than 710 μm has an ethylene content equal to 18.7%. The amount of Atmer163 determined from nitrogen analysis of the large fraction (>710 μm) was 580ppm, while the amount determined from analysis of the fine fraction (<710 μm) was 4060 ppm.
With the same equipment and producing the same product, running for a total of 6 days, there were no fouling problems in the reactor or any other process equipment.
The same test was run under the same conditions and in the absence of Atmer, and was discontinued after about 1 day, with blockages occurring in both the gas distribution decking and the polymer discharge line. Example 13
LLDPE was prepared using a pilot plant continuous operation. Device (illustrated in FIG. 2)Comprising a prepolymerization reactor R1Into this reactor, MgCl, containing 45% by weight of ethanol, according to the general method indicated above, is introduced2-a solid catalyst component prepared from an ethanol adduct, a solution of an aluminum alkyl in an inert hydrocarbon, an electron donor compound and a small amount of propylene (line 1). At the rear of this section, the reaction is carried out in a series of gas-phase reactors R2And R3From the polymerization reactor (line 3), consisting of a slurry of the prepolymer (polypropylene) in an inert liquid, is contacted with a stream of Atmer163 in a determined ratio with the aluminium alkyl (line 2) and is subsequently fed to the second stageA gas-phase polymerization section.
The reaction monomers fed through line 4 are as follows: ethylene and butylene; hydrogen as molecular weight regulator. The product is discharged from the second gas phase reactor via line 5. The temperature of the main operation condition is 25 ℃; residence time 87 minutes first gas phase reactor temperature 75 ℃; pressure 1800 kPa (18 bar); Atmer/TEAL 0.5 (by weight); h2／C20.16 (mole); c4／(C2+C4) 0.118 (mole); the temperature of the second gas phase reactor is 75 ℃; pressure 1700 kpa (17 bar); h2／C20.213 (mole); c4／(C2+C4) 0.134 (mole);final characteristics of the product
The true density is 0.919 kg/L; melt index "E" 1.1 g/10 min
The average polymer production rate was 75 kg/h.
The same type of product was produced with the same apparatus, which was operated for about 9 days with absolute reliability. Example 14
The LLDPE was prepared in a continuous operation using a pilot plant. The plant (illustrated in FIG. 2) comprises a prepolymerization reactor R1Into this reactor, MgCl containing 45% by weight of ethanol is introduced (via line 1) in the general manner described below2-a solid catalyst component prepared from an ethanol adduct, a solution of an aluminium alkyl in an inert hydrocarbon, an electron donor compound and a small amount of propylene. At the end of this section, the reaction is carried out in two gas-phase reactors R connected in series2And R3The process is carried out. The stream coming out of the polymerization reactor (line 3), consisting of a slurry of the prepolymer (polypropylene) in an inert liquid, is brought into contact with a stream of Atmer163 in a determined ratio with the aluminium alkyl (line 2) and is subsequently sent to the first gas-phase polymerization stage.
The reaction monomers fed through line 4 are as follows: ethylene and butylene; hydrogen as molecular weight regulator.
The product is prepared byThe two gas phase reactors are discharged via line 5.Main operating conditions prepolymerization step R1The temperature is 25 ℃; residence time 137 minutes first gas phase reactor temperature 70 ℃; pressure 1800 kPa (18 bar); Atmer/TEAL 0.5 (by weight); h2／C20.36 (mole); c4／(C2+C4) 0.21 (mole); propane/C21.54 (mole); the temperature of the second gas phase reactor is 70 ℃; pressure 1500 kPa (15 bar); h2／C20.346 (mole); c4／(C2+C4) 0.275 (mol); propane/C20.784 (mol); the final characteristic true density of the product is 0.909 kg/L; melt index "E" 2.1 g/10 min
The average polymer production rate was 63 kg/h.
The same apparatus was used to produce the same type of product, and the apparatus was operated for about 9 days under the condition of absolute reliability.
TABLE 1
Figure 9310267600241
Figure 9310267600251

Claims (16)

1. Production of olefin CH2Process for the (co) polymerization of CHR, in which R is hydrogen or an alkyl or aryl group having 1 to 10 carbon atoms, comprising at least one gas-phase (co) polymerization step carried out in a fluidized or stirred bed in the presence of a catalyst comprising the reaction product of (1) a solid component of a titanium compound supported on a magnesium dihalide in active form, optionally containing an internal electron donor, and (2) an alkylaluminum compound, optionally in the presence of an external electron donor, characterized in that(ii) containing particulate polymer particles in said fluidized or stirred bed, at least 80% of which are greater than 500 μm and less than 10% of which are less than 200 μm; and a compound (3) having a chain of at least 4 carbon atoms and containing at least two identical or different groups capable of reacting with the alkylaluminum compound (2) is added at any stage of the process, in an amount greater than 100ppm by weight of said (co) polymer, the molar ratio of compound (3) to said alkylaluminum compound (2) being less than 1; the compound (3) is selected to inhibit polymerization on polymer particles smaller than 850 μm when used in standard polymerization tests of mixtures of ethylene and propylene.
2. The process according to claim 1, characterized in that the compound (3) is selected from compounds belonging to one of the following classes:
(a) a polyol containing a chain of 4 to 8 carbon atoms;
(b) a hydroxy ester containing at least two free hydroxy groups and prepared from a carboxylic acid of 8 to 22 carbon atoms and a polyol;
(c) has the general formula
CH3(CH2)nCH2-N(CH2CH2OH)2N-alkyl diethanol amines of (1), wherein N is greater than 2;
(d) polyepoxide unsaturated oils.
3. A process according to claim 2, characterized in that the compound (3) is selected from the group consisting of 1, 4-butanediol, sorbitol, glycerol-monostearate, sorbitan-monooleate, epoxidized linseed oil, epoxidized soya oil, of the formula
CH3(CH2)nCH2-N(CH2CH2OH)2Wherein N is 6 to 20.
4. Process according to claim 1, characterized in that the compound (3) is added in an amount of 100-2000ppm relative to the weight of the final polymer and the molar ratio of the compound (3) to the alkylaluminum compound is between 0.05 and 0.8.
5. The process according to claim 1, characterized in that the alkane having 3 to 5 carbon atoms is present in the gas phase in a molar concentration comprised between 20 and 90% of the total gas.
6. A process according to claim 5, characterized in that the alkane is propane.
7. A process according to claim 1, characterized in that the titanium compound comprises at least one halide-Ti bond.
8. Process according to claim 1, characterized in that the solid component comprises an internal electron donor and the reaction is carried out in the presence of an external electron donor.
9. Process according to claim 1, characterized in that theinternal electron donor compound is a diether having the formula:wherein R isⅠAnd RⅡIdentical or different from each other, are alkanes having 1 to 18 carbon atomsAlkyl, cycloalkyl and aryl, and, RⅢAnd RⅣThe same or different from each other, are alkyl groups of 1 to 4 carbon atoms.
10. The process according to claim 8, characterized in that the solid component (1) is spherical.
11. The process according to claim 9, characterized in that the solid component (1) is spherical.
12. The product of the process according to any one of claims 1 to 11.
13. A particulate olefin polymer obtainable by a process according to any one of claims 1 to 9, characterized in that the compound (3) is aggregated on polymer particles smaller than 700 μm.
14. A spherical olefin polymer obtained by the process of claim 10, wherein the compound (3) is aggregated on polymer particles of less than 700 μm.
15. Ethylene (co) polymers obtained by the process according to claim 1, characterized in that the compound (3) is aggregated on polymer particles smaller than 700 μm.
16. Propylene (co) polymers obtainable by the process according to claim 8 or 9, characterized in that the compound (3) is aggregated on polymer particles as small as 700 μm.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105431462A (en) * 2013-01-14 2016-03-23 巴塞尔聚烯烃意大利有限公司 Process for the preparation of ethylene polymers

Families Citing this family (138)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW354792B (en) 1993-08-13 1999-03-21 Mitsui Petrochemical Ind Olefin polymerization catalyst and process for preparing polypropylene and propylene block copolymer
ATE167878T1 (en) † 1993-09-16 1998-07-15 Union Carbide Chem Plastic PRODUCTION OF POLYMERS
US6140432A (en) * 1995-07-13 2000-10-31 Exxon Chemical Patents Inc. Polymerization catalyst systems, their production and use
US6124230A (en) * 1995-07-13 2000-09-26 Exxon Chemical Patents, Inc. Polymerization catalyst systems, their production and use
FI105818B (en) * 1996-03-13 2000-10-13 Borealis Tech Oy Process for the polymerization of olefin monomers
US6191239B1 (en) 1998-02-18 2001-02-20 Eastman Chemical Company Process for producing polyethylene
US6271321B1 (en) 1998-02-18 2001-08-07 Eastman Chemical Company Process for producing polyethylene
US6534613B2 (en) 1998-02-18 2003-03-18 Eastman Chemical Company Process for producing polyethylene
US6228957B1 (en) 1998-02-18 2001-05-08 Eastman Chemical Company Process for producing polyethlene
US6245868B1 (en) 1998-05-29 2001-06-12 Univation Technologies Catalyst delivery method, a catalyst feeder and their use in a polymerization process
US7354880B2 (en) * 1998-07-10 2008-04-08 Univation Technologies, Llc Catalyst composition and methods for its preparation and use in a polymerization process
US6291613B1 (en) 1998-10-27 2001-09-18 Eastman Chemical Company Process for the polymerization of olefins
ATE388967T1 (en) 1998-10-27 2008-03-15 Westlake Longview Corp METHOD FOR POLYMERIZING OLEFINS; POLYETHYLENE, AND FILMS, AND ITEMS MADE THEREFROM
US20040138057A1 (en) * 1998-12-21 2004-07-15 Wenzel Timothy T. Catalyst composition and methods for its preparation and use in a polymerization process
CN1177869C (en) 1999-03-30 2004-12-01 伊斯曼化学公司 Process for producing polyolefins
US6300432B1 (en) 1999-03-30 2001-10-09 Eastman Chemical Company Process for producing polyolefins
US6417299B1 (en) 1999-06-07 2002-07-09 Eastman Chemical Company Process for producing ethylene/olefin interpolymers
US6359083B1 (en) 2000-05-02 2002-03-19 Eastman Chemical Company Olefin polymerization process
US6593267B2 (en) 2000-12-18 2003-07-15 Univation Technologies, Llc Method for preparing a supported catalyst system and its use in a polymerization process
US6933258B2 (en) * 2000-12-19 2005-08-23 Univation Technologies, L.L.C. Catalyst composition and methods for its preparation and use in a polymerization process
US6884749B2 (en) 2002-10-17 2005-04-26 Equistar Chemicals L.P. Supported catalysts which reduce sheeting in olefin polymerization, process for the preparation and the use thereof
EP1611169B1 (en) * 2003-03-21 2010-06-02 Dow Global Technologies Inc. Morphology controlled olefin polymerization process
EP1668049B1 (en) 2003-09-23 2015-02-25 Dow Global Technologies LLC Catalyst composition for ethylene polymerization
KR101114748B1 (en) † 2003-09-23 2012-03-05 다우 글로벌 테크놀로지스 엘엘씨 Self limiting catalyst composition and propylene polymerization process
US20050148742A1 (en) * 2004-01-02 2005-07-07 Hagerty Robert O. Method for controlling sheeting in gas phase reactors
US7985811B2 (en) 2004-01-02 2011-07-26 Univation Technologies, Llc Method for controlling sheeting in gas phase reactors
US20070073012A1 (en) * 2005-09-28 2007-03-29 Pannell Richard B Method for seed bed treatment before a polymerization reaction
US7754830B2 (en) 2004-05-20 2010-07-13 Univation Technologies, Llc Polymerization reaction monitoring with determination of induced condensing agent concentration for preventing discontinuity events
US7683140B2 (en) * 2004-05-20 2010-03-23 Univation Technologies, Llc Method for determining temperature value indicative of resin stickiness from data generated by polymerization reaction monitoring
EP1749034A2 (en) * 2004-05-20 2007-02-07 Univation Technologies, LLC Gas olefin polymerization process
DE602006010027D1 (en) 2005-02-03 2009-12-10 Basell Poliolefine Srl PROPYLENE POLYMER COMPOSITION FOR INJECTION MOLDING
BRPI0612441A2 (en) 2005-05-12 2010-11-23 Basell Poliolefine Srl propylene ethylene copolymers and process for their preparation
PL1888653T3 (en) * 2005-06-07 2016-08-31 Saudi Basic Ind Corp Process for the polymerization of olefins
CN101213249B (en) 2005-07-01 2012-02-01 巴塞尔聚烯烃意大利有限责任公司 Propylene polymers having broad molecular weight distribution
WO2008018976A1 (en) * 2006-08-04 2008-02-14 Univation Technologies, Llc Method of maintaining heat transfer capacity in a polymerization reaction system
US8273834B2 (en) * 2006-09-07 2012-09-25 Univation Technologies, Llc Methods for determining temperature value indicative of resin stickiness from data generated by polymerization reaction monitoring
RU2448981C2 (en) * 2006-09-07 2012-04-27 Юнивейшн Текнолоджиз, Ллк Methods for real-time determination of degree of resin stickiness using model for depression of melt initiation temperature
BRPI0605781A (en) 2006-12-29 2008-08-19 Braskem Sa antistatic composition for gas phase olefin polymerization or copolymerization, gas phase olefin polymerization or copolymerization process, and thus obtained olefin polymer or copolymer
US7402636B1 (en) * 2007-03-23 2008-07-22 Exxonmobil Chemical Patents Inc Method and apparatus for decreasing polymer deposition
US8981021B2 (en) * 2007-03-30 2015-03-17 Univation Technologies, Llc Systems and methods for fabricating polyolefins
TW200909449A (en) * 2007-07-18 2009-03-01 Basell Poliolefine Srl Process for the polymerization of olefins
US20100273641A1 (en) 2007-12-21 2010-10-28 Linfeng Chen Self-Limiting Catalyst Composition with Non-Phthalate Internal Donor
EP2090357B1 (en) 2007-12-24 2018-04-04 Borealis Technology OY Reactor system and process for the catalytic polymerization of olefins, and the use of such reactor system in catalytic polymerization of olefins
EP2082797A1 (en) 2007-12-24 2009-07-29 Borealis Technology OY Reactor system for the catalytic polymerization of olefins comprising shielding means and a process and use thereof
EP2090356A1 (en) 2007-12-24 2009-08-19 Borealis Technology OY Reactor systems and process for the catalytic polymerization of olefins, and the use of such reactor system in catalytic polymeration of olefins
US20100292418A1 (en) * 2007-12-31 2010-11-18 Dow Global Technologies Inc. Process for polymerizing olefin-based polymers
EP2130863A1 (en) 2008-06-02 2009-12-09 Borealis AG High density polymer compositions, a method for their preparation and pressure-resistant pipes made therefrom
EP2130862A1 (en) 2008-06-02 2009-12-09 Borealis AG Polymer compositions and pressure-resistant pipes made thereof
EP2130859A1 (en) 2008-06-02 2009-12-09 Borealis AG Polymer compositions having improved homogeneity and odour, a method for making them and pipes made thereof
EP2294095B1 (en) * 2008-06-26 2013-03-20 Basf Corporation Process for the production of an alpha-olefin polymer
EP2182524A1 (en) 2008-10-31 2010-05-05 Borealis AG Cable and Polymer composition comprising a multimodal ethylene copolymer
EP2182525A1 (en) 2008-10-31 2010-05-05 Borealis AG Cable and polymer composition comprising a multimodal ethylene copolymer
EP2182526A1 (en) 2008-10-31 2010-05-05 Borealis AG Cable and polymer composition comprising an multimodal ethylene copolymer
ATE551369T1 (en) 2008-11-17 2012-04-15 Borealis Ag MULTI-STEP PROCESS FOR PRODUCING POLYETHYLENE WITH REDUCED GEL FORMATION
ATE529450T1 (en) 2009-02-25 2011-11-15 Borealis Ag MULTIMODAL PROPYLENE POLYMER, COMPOSITION THEREOF AND METHOD FOR PRODUCING THEREOF
EP2223944A1 (en) 2009-02-26 2010-09-01 Borealis AG Process for producing semicrystalline propylene polymers
EP2287212B1 (en) 2009-08-21 2014-03-26 China Petroleum & Chemical Corporation A catalyst component for ethylene polymerization, preparation thereof and a catalyst comprising the catalyst component
CN102741301B (en) * 2009-09-11 2014-10-08 巴塞尔聚烯烃意大利有限责任公司 Process for the gas-phase polymerization of olefins
US8603933B2 (en) 2009-11-13 2013-12-10 Borealis Ag Process for recovering a transition metal compound
US8501881B2 (en) 2009-11-13 2013-08-06 Borealis Ag Process for olefin polymerization
EP2499168B1 (en) 2009-11-13 2017-05-10 Borealis AG Process for recovering a transition metal compound
EP2322568B1 (en) 2009-11-13 2013-05-15 Borealis AG Process for producing an olefin polymerization catalyst
EP2519549A1 (en) 2009-12-29 2012-11-07 Basell Poliolefine Italia S.r.l. Process for the production of polyolefin films
EP2397221B1 (en) 2010-06-17 2017-04-12 Borealis AG Control system for a gas phase reactor, a gas phase reactor for catalytic production of polyolefines, a method for catalytic productions of polyolefines and a use of the control system
BR112013007376B1 (en) 2010-09-28 2020-07-28 Basell Polyolefine Gmbh method for feeding an antistatic compound to a polymerization reactor, catalyst suspension, its use and process for the polymerization of olefins
RU2584694C2 (en) 2010-09-28 2016-05-20 Базелль Полиолефине Гмбх Polyethylene extruded articles
BR112013006169B1 (en) 2010-09-28 2020-02-11 Basell Polyolefine Gmbh METHOD FOR FEEDING AN ANTISTATIC COMPOUND TO A POLYMERIZATION REACTOR, CATALYTIC PASTE, ITS USE AND PROCESS FOR THE POLYMERIZATION OF OLEFINS
EP2452957A1 (en) 2010-11-12 2012-05-16 Borealis AG Improved process for producing heterophasic propylene copolymers
EP2452959B1 (en) 2010-11-12 2015-01-21 Borealis AG Process for producing propylene random copolymers and their use
EP2452960B1 (en) 2010-11-12 2015-01-07 Borealis AG Process for preparing propylene polymers with an ultra high melt flow rate
EP2452976A1 (en) 2010-11-12 2012-05-16 Borealis AG Heterophasic propylene copolymers with improved stiffness/impact/flowability balance
CA2820359C (en) 2010-12-20 2019-10-22 Braskem America, Inc. Propylene-based compositions of enhanced appearance and excellent mold flowability
ES2605429T3 (en) 2011-06-15 2017-03-14 Borealis Ag Mixing the in situ reactor of a nucleated polypropylene catalyzed by Ziegler-Natta and a metallocene catalyzed polypropylene
EP2570455A1 (en) 2011-09-16 2013-03-20 Borealis AG Polyethylene composition with broad molecular weight distribution and improved homogeneity
EP2583998B1 (en) 2011-10-21 2018-02-28 Borealis AG Polyethylene composition with high rapid crack propagation resistance and pressure resistance
EP2594333B1 (en) 2011-11-21 2014-07-30 Borealis AG Method for recovering polymer and apparatus therefor
EP2599828A1 (en) 2011-12-01 2013-06-05 Borealis AG Multimodal polyethylene composition for the production of pipes with improved slow crack growth resistance
EP2617741B1 (en) 2012-01-18 2016-01-13 Borealis AG Process for polymerizing olefin polymers in the presence of a catalyst system and a method of controlling the process
EP2620472B1 (en) 2012-01-24 2018-05-30 Borealis AG Poyethylene composition with improved low temperature perssure resistance
EP2711379A1 (en) 2012-09-21 2014-03-26 Basell Poliolefine Italia S.r.l. Process for the gas-phase polymerization of olefins
EP2722347A1 (en) * 2012-10-22 2014-04-23 Basell Polyolefine GmbH Multistage process for the polymerization of olefins
EP2730611B1 (en) 2012-11-09 2017-01-04 Abu Dhabi Polymers Company Limited (Borouge) Drip irrigation pipe comprising a polymer composition comprising a multimodal polyethylene base resin
ES2604934T3 (en) 2012-11-09 2017-03-10 Abu Dhabi Polymers Company Limited (Borouge) Polymeric composition comprising a mixture of a multimodal polyethylene and an additional ethylene polymer suitable for the manufacture of a drip irrigation tube
EP2740761B1 (en) 2012-12-05 2016-10-19 Borealis AG Polyethylene composition with improved balance of slow crack growth resistance, impact performance and pipe pressure resistance for pipe applications
EP2749580B1 (en) 2012-12-28 2016-09-14 Borealis AG Process for producing copolymers of propylene
EP2796473B1 (en) 2013-04-22 2017-05-31 Borealis AG Multistage process for producing low-temperature resistant polypropylene compositions
EP3235832B1 (en) 2013-04-22 2018-06-20 Borealis AG Polypropylene compositions
PL2796501T3 (en) 2013-04-22 2017-01-31 Abu Dhabi Polymers Company Limited (Borouge) Multimodal polypropylene composition for pipe applications
TR201808436T4 (en) 2013-04-22 2018-07-23 Abu Dhabi Polymers Co Ltd Borouge Polypropylene composition with improved impact strength for pipe applications.
EP2796472B1 (en) 2013-04-22 2017-06-28 Borealis AG Two-stage process for producing polypropylene compositions
PL2796498T3 (en) 2013-04-22 2019-03-29 Abu Dhabi Polymers Company Limited (Borouge) Multimodal polypropylene composition for pipe applications
PL2796500T3 (en) 2013-04-22 2018-12-31 Abu Dhabi Polymers Company Limited (Borouge) Propylene random copolymer composition for pipe applications
EP2842912A1 (en) 2013-08-26 2015-03-04 Basell Poliolefine Italia S.r.l. Method for improving the operability of an olefin polymerization reactor
EP2853562A1 (en) 2013-09-27 2015-04-01 Borealis AG Two-stage process for producing polypropylene compositions
EP2860203B1 (en) 2013-10-10 2016-12-14 Borealis AG Multistage process for producing polyethylene compositions
EP2860200B1 (en) 2013-10-10 2017-08-02 Borealis AG Polyethylene composition for pipe and pipe coating applications
EP2860204B1 (en) 2013-10-10 2018-08-01 Borealis AG Polyethylene composition for pipe applications
EP2860202B1 (en) 2013-10-10 2018-05-30 Borealis AG High temperature resistant polyethylene and process for the production thereof
EP2860201A1 (en) 2013-10-10 2015-04-15 Borealis AG High temperature resistant polyethylene and process for the production thereof
CN105683279B (en) 2013-10-30 2019-08-09 阿布扎比聚合物有限公司(博禄) Polyethylene composition suitable for injection molding application
ES2687899T3 (en) * 2013-11-15 2018-10-29 Dow Global Technologies Llc Catalyst composition and polymerization method that uses it
EP2883887A1 (en) 2013-12-13 2015-06-17 Borealis AG Multistage process for producing polyethylene compositions
EP2883885A1 (en) 2013-12-13 2015-06-17 Borealis AG Multistage process for producing polyethylene compositions
ES2660121T3 (en) 2013-12-20 2018-03-20 Borealis Ag Polyethylene composition with high flexibility and high temperature resistance, suitable for tube applications
EP2894195B1 (en) 2013-12-23 2016-09-14 Abu Dhabi Polymers Company Limited (Borouge) Polyethylene composition for pipe applications with improved sagging properties
CN106715067A (en) 2014-12-08 2017-05-24 博里利斯股份公司 Process for producing pellets of copolymers of propylene
ES2944941T3 (en) 2015-02-05 2023-06-27 Borealis Ag Procedure for producing polyethylene
BR112017016081B1 (en) 2015-02-20 2022-05-03 Borealis Ag Propylene heterophasic copolymers, their production process and pipe
EP3274376B1 (en) 2015-03-26 2018-06-20 Basell Polyolefine GmbH Polymerization process in the presence of antistatic agent
EP3088458B2 (en) 2015-04-27 2022-10-05 Abu Dhabi Polymers Company Limited (Borouge) L.L.C. Polyethylene composition suitable for pipe applications
EP3109275B1 (en) 2015-06-22 2017-08-09 Abu Dhabi Polymers Company Limited (Borouge) L.L.C. Polyethylene composition for pipe applications with improved sagging and extrusion properties
EP3109261B1 (en) 2015-06-23 2018-12-26 Borealis AG Process for producing lldpe resins
WO2017108337A1 (en) 2015-12-21 2017-06-29 Basell Poliolefine Italia S.R.L. Olefin polymerization process in the presence of antistatic composition
EP3238938A1 (en) 2016-04-29 2017-11-01 Borealis AG Machine direction oriented films comprising multimodal copolymer of ethylene and at least two alpha-olefin comonomers
WO2017207493A1 (en) 2016-05-31 2017-12-07 Borealis Ag Polymer composition and a process for production of the polymer composition
EP3252085B1 (en) 2016-05-31 2022-11-09 Borealis AG Jacket with improved properties
WO2017220558A1 (en) 2016-06-22 2017-12-28 Borealis Ag Polymer composition and a process for production of the polymer composition
BR112019002951B1 (en) 2016-11-25 2022-12-20 Borealis Ag POLYMER COMPOSITION, ARTICLE, USE OF POLYETHYLENE COMPOSITION, AND PROCESS FOR PRODUCING A POLYMER COMPOSITION
EP3418330B2 (en) 2017-06-21 2023-07-19 Borealis AG Polymer composition and a process for production of the polymer composition
CN109135067A (en) 2017-06-27 2019-01-04 阿布扎比聚合物有限责任公司(博禄) For manufacturing the polypropene composition of high-voltage tube
EP3480220A1 (en) * 2017-11-06 2019-05-08 Borealis AG Combined sequential parallel reactor configuration
KR20210033017A (en) 2018-07-19 2021-03-25 보레알리스 아게 Method for producing ultra-high molecular weight polyethylene homopolymer
WO2020069853A1 (en) 2018-10-02 2020-04-09 Sabic Global Technologies B.V. Method for the manufacture of a polyolefin compound
US20210317290A1 (en) 2018-10-31 2021-10-14 Borealis Ag Polyethylene composition for high pressure resistant pipes with improved homogeneity
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WO2020109289A1 (en) 2018-11-28 2020-06-04 Abu Dhabi Polymers Co. Ltd (Borouge) L.L.C. Polyethylene composition for film applications
US10781273B2 (en) * 2018-12-27 2020-09-22 Chevron Phillips Chemical Company Lp Multiple reactor and multiple zone polyolefin polymerization
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AU2020316600B2 (en) 2019-07-22 2023-11-30 Abu Dhabi Polymers Co. Ltd (Borouge) L.L.C. Single site catalysed multimodal polyethylene composition
EP4025614A1 (en) 2019-09-05 2022-07-13 ExxonMobil Chemical Patents Inc. Processes for producing polyolefins and impact copolymers with broad molecular weight distribution and high stiffness
WO2021080813A1 (en) 2019-10-22 2021-04-29 Exxonmobil Chemical Patents Inc. Thermoplastic vulcanizate compositions and processes for the production thereof
WO2021080803A1 (en) 2019-10-22 2021-04-29 Exxonmobil Chemical Patents Inc. Impact copolymer compositions
EP3835327A1 (en) 2019-12-09 2021-06-16 Borealis AG System for producing polyolefin and process for recovering polymerization product from gas phase reactor
EP4093780A1 (en) 2020-01-24 2022-11-30 ExxonMobil Chemical Patents Inc. Methods for producing bimodal polyolefins and impact copolymers
EP4107196A1 (en) 2020-02-17 2022-12-28 ExxonMobil Chemical Patents Inc. Propylene-based polymer compositions having a high molecular weight tail
EP4019583B1 (en) 2020-12-28 2024-04-10 ABU DHABI POLYMERS CO. LTD (BOROUGE) - Sole Proprietorship L.L.C. Polyethylene composition for film applications with improved toughness and stiffness
EP4335877A1 (en) 2022-09-09 2024-03-13 Basell Polyolefine GmbH Continuous olefin polymerization process in the presence of an antistatic agent
CN116333193B (en) * 2023-05-22 2024-02-02 上海优铖工逸技术有限公司 Ziegler Natta catalyst, preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0359444A1 (en) * 1988-09-13 1990-03-21 BP Chemicals Limited Gas-phase alpha-olefin polymerization process in the presence of an activity retarder
EP0362629A2 (en) * 1988-10-01 1990-04-11 BASF Aktiengesellschaft Avoidance of coloured contaminations during the preparation of ultra-high molecular weight polyethylenes by means of a catalyst containing titanium

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL137126C (en) * 1961-09-28
DK133012C (en) * 1968-11-21 1976-08-09 Montedison Spa CATALYST FOR POLYMERIZATION OF ALKENES
YU35844B (en) * 1968-11-25 1981-08-31 Montedison Spa Process for obtaining catalysts for the polymerization of olefines
NL190723C (en) * 1975-06-12 1994-07-18 Montedison Spa Process for preparing Ziegler catalysts for the polymerization of olefins.
IT1078995B (en) * 1977-05-24 1985-05-08 Montedison Spa CATALYSTS FOR THE POLYMERIZATION OF OLEFINE
IT1150650B (en) * 1982-03-10 1986-12-17 Montedison Spa FLUID BED REACTOR
US4526943A (en) * 1982-07-29 1985-07-02 The Dow Chemical Company Process for polymerizing olefins in the presence of a catalyst prepared from organomagnesium compound, organic hydroxyl-containing compound, reducing halide source and transition metal compound
JPS6067508A (en) * 1983-09-22 1985-04-17 Toa Nenryo Kogyo Kk Polymerization of olefin
CA1235543A (en) * 1984-09-12 1988-04-19 Norio Kashiwa Process for producing propylene block copolymer
DE3501858A1 (en) * 1985-01-22 1986-07-24 Neste Oy, Espoo CATALYST COMPONENTS, CATALYST AND METHOD FOR THE POLYMERIZATION OF OLEFINS
EP0241560B1 (en) * 1985-10-11 1991-04-03 Sumitomo Chemical Company, Limited Catalyst for olefin polymerization and process for preparing olefin polymer by using the same
DE3600610A1 (en) * 1986-01-11 1987-07-16 Basf Ag USE OF ANTISTATICS TO PREVENT COATING IN THE PRODUCTION OF ETHYLENE POLYMERISATS IN GAS PHASE REACTORS
DE3600611A1 (en) * 1986-01-11 1987-07-16 Basf Ag USE OF ANTISTATICS TO PREVENT COATING IN THE PRODUCTION OF ULTRA HIGH MOLECULAR POLYETHYLENE IN GAS PHASE REACTORS
US4803251A (en) * 1987-11-04 1989-02-07 Union Carbide Corporation Method for reducing sheeting during polymerization of alpha-olefins
FR2634212B1 (en) * 1988-07-15 1991-04-19 Bp Chimie Sa APPARATUS AND METHOD FOR POLYMERIZATION OF GASEOUS OLEFINS IN A FLUIDIZED BED REACTOR
DE3833444A1 (en) * 1988-10-01 1990-04-05 Basf Ag PREVENTION OF COLORED IMPURITIES IN THE PRODUCTION OF ULTRA HIGH-MOLECULAR ETHYLENE POLYMERISATES BY MEANS OF A TITANIUM-CONTAINING CATALYST SYSTEM
FR2658498B1 (en) * 1990-02-19 1992-05-15 Atochem MAGNESIUM CHLORIDE PARTICLES WITH CONICAL TRUNK STRUCTURE, CATALYTIC COMPONENT SUPPORTED ON THESE PARTICLES, POLYOLEFINS OBTAINED FROM THIS CATALYTIC COMPONENT, METHODS OF MANUFACTURE THEREOF.
US5036480A (en) * 1990-03-12 1991-07-30 Honeywell Inc. Method and apparatus for simulating microburst windshears
JPH04202406A (en) * 1990-11-30 1992-07-23 Ube Ind Ltd Polymerization and copolymerization of ethylene

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0359444A1 (en) * 1988-09-13 1990-03-21 BP Chemicals Limited Gas-phase alpha-olefin polymerization process in the presence of an activity retarder
EP0362629A2 (en) * 1988-10-01 1990-04-11 BASF Aktiengesellschaft Avoidance of coloured contaminations during the preparation of ultra-high molecular weight polyethylenes by means of a catalyst containing titanium

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105431462A (en) * 2013-01-14 2016-03-23 巴塞尔聚烯烃意大利有限公司 Process for the preparation of ethylene polymers
CN105431462B (en) * 2013-01-14 2018-01-26 巴塞尔聚烯烃意大利有限公司 Polyvinyl preparation method

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